Method of making moldable thermosetting compositions



Patented 1 Jan. 26, "1943 E T PATENT OFFICE 2,809,842

m-z'rnon or MAKING momsnui mimo- I sa'rrmc courosrnous m repent, Miami, Fla, and Sydney n. Hall,

Kenmore, and Lothar A. Sontag, North T Olllwands, N. Y., assignors to. Durex Plaotic's & Chemicals, Inc.. North Tonawanda, N. Y.

Serial No. 297,546

No Drawing. simulation October a, 1m,

30laims. ious -ssi" The present invention, relates to a method of making moldable thermosetting composition and more particularly a comparatively dense, solid mixture of thermosetting resinand filler capable of being molded.

Heretofore, in the'preparation oi molded ari'orm' that can be readily placed in a preiorming machine or mold and which will fiow readily thereinto with the production of a desirably preformed object or article.

7 ticles wherein a thermosetting resin is used as the basis of the molded article, it has been customary to include filler, of either organic or inorganic nature, in the composition to be molded.

It has also been general practice to prepare powdered mixtures or resin bond and filler as-so-called molding compounds. In certain instances, dry powdered resin and dry powdered filler were mixed and the mixture sold as molding compound (Ellis, The Chemistry oi Synthetic Resins, 1935, page 1278) A disadvantage of this type oi compound resides in the possi- In accordance with the procedures of the presmachines may be employed, such as those oi the bility oi shaking out" with some separation of the bond and filler prior to use, thus producing non-uniformity in the composition. In other instances the mixture of filler and resin was passed through hot rollers to produce sheets which were subsequently ground. 'Many disadvantages attend this procedure (Ellis, page 1280),

In the production of certain kinds of molding compounds wherein it is desirable to use fillers containing relatively long fibers, the long fibers produced what are known as whiskers upon grinding rolled sheets, showing poor coverage of the filler and .producing a fiuiiy powder i'rom' which a poor fiow into preiorming cavities was obtained. and in many instances poorly molded eration about to be described in detail.

' may be employed, as for instance, toluol, alcohol, v I

well known Wemer-Pfieider type.

In general, the fluid admixedwith the thermosetting resin will be water, although in special cases, other fluids volatile below about 110 C.

acetone and the like. 4 recommended procedure is to prepare the resinin an aqueous environment and mix the filler with the aqueous reaction mixture. However, when special eiiects are desired or where several types or thermosetting resinare included in the bond, non-aqueous solvents find application. The quantity of water or other fiuid employed will be sumcient to render the mix fiowable and also su'flicient to absorb the irictional heat generated in a subsequent op- In general the liquid will be at least 10% of the mixture and in many instances' will 'preierably bejabout products resulted. Furthermore; due to pooi coverage or filler, spots oiten occurred in the as final article upon bufiing oi! the fins. I

It is an object of the present invention to pre-' pare a moldable compound having a thermosetting bond and a filler wherein no separation oil resin'and fiber is produced and wherein a uni form relation between resin and fiber is maintained at al Itimes with consequent production r uniformity of finishedhnolded article.

The present invention also provides a molding y compositioncapable of being preformed and in which good coverage of filler is obtained.

, Additionally, the invention provides an excellent means'ior producing high density molding compositions of the thermosetting type in which long fiber filler is incorporated with the resin and in consequence of which articles of high'impact strength 'are capable oi. production in, molds of relatively less depth.

' trurthermore, the'present invention provides If 8 111811 density. 1110mm composition pellet 55 bmtel'inl WOilld'bQ the production After on; liquid thennosettins resin and mo filler have been uniformly mixed, the resultant plastic compound isthen extruded through a suitable orifice and formed into rods. the thickness or'diameteroi which is at least equal to the fiber length oi the filler. Bymeans'oi this extrusion, it is. believed that fiowoi the plastic mass is induced with a substantial orientation .0! fibers "parallel to the motion of flow through the extrusion orifice, thus making a substantial number of the fibers parallel to the lengthwise dimension oi the rod.

The extrudedrods-may be iormed'in any desired shape and length and in general may be from ot an inch in length to several 'ieet in length, although thisJs purely a matter controlledby subsequent use of the molding com pound. I '1 The. rods, as formed in with the above procedure, still contain considerable quantities oi liquid, which, in many instances, would be objectionable in amolding compound since of the mixture.

. and a reflux cohdenser:

' machine m passed through round orifices it of a poorly molded product. This residual liquid is, therefore, removed from the molding compound by any suitable means, as, for instance,

under vacuum or by drying at a relatively elevated temperature and in such fashion as to remove the enclosed moisture rapidly without producing any considerable advancement or cure of the thermosetting resin bond.

In one method of operation the rods are passed into and'rapidlythrougha heated zone of consubstantial flash evaporation of moisture with-. out greatly increasing the internal temperature when dry, the rods are hard, dense pellets that can be readily placed ln-a preforming mold, and due to theirrelatively dense nature when prepared for long flbered filler, the gmoldsfor producing a given article may be substantially shallower than those required heretofore for producing the same article from molding 20 powder made from sheets.-

As a specific illustration of the invention which is .not to be deemed limitative thereof, a form of liquid resin suitable for admixture with fillerin the. manner above described is a. one-step phenol aldehyde resin made from the following formulation:

Poundscool very quickly in the open air, moisture being trolled humidity suitable for inducing a rapid or in diameter. The extruded product is obtained in the. form of small, compact rods about in diameter. During extrusion, heat is generated and the rods come from the extruder at about 100 C. Due to their large surface area, they evaporated during the process.

The rods are then dried for about" fifteen minutes at 90 C. in a current of air. The product is then broken up to pass a four mesh screen and is ready for molding. The apparent density v of the material is 0.285. gm. pe'r c'c.

The flufl'y powder taken from the mixer if dried directly in exactly the same way, is moldable but has an apparent density of only'0.190.

Crude phenol 100 Formaldehyde (37% aqueous solution) 100 The above mixture is boiled until chemical reaction occurs with the production of a liquid emulsion ofxresin and water. This liquid resin containing very large proportions of water and entirely unsuited for molding practices as performed heretofore, is then mixed uniformly with the filler. The resultant mixture contains about 40% water, although anywhere from 8% to about- 80% water may be present.- Notwithstanding the large quantity of water, the mixture possesses thermosetting characteristics. The plastic mixture is then extruded through an orifice of the.

desired diameter and formed into flexible rods. During the extrusion process, some moisture is lost but a considerable proportion still remains in the extruded rods which moisture is subsequently removed by controlled evaporation under coiiditionssuitable for removing moisture with out inducing any considerable advancement of the resin.

Example 2.

The following solution is prepared and heated to boiling in a .vessel provided with an agitator 7 Soon after boiling begins a liquid resin separates from the solution. The mixture is boiled for t-hour longer during which time the separated resin becomes a viscous liquid. The mixture of liquid resin and water is added to the mixer containing f Grams Wood flour (ground to pass 20 'mesh) 1200 Zinc stearate 24 Mixing is continued for about fifteen minutes to Example 3 A resin is prepared according to Dent (U. S.

The mixtur'eis heated to\boiling anda resinous phase separates almost as soon asboiling temperature is reached. I The following solution is carefully added: I

, Grams Ammonium sulfate 9 Hexamethylene tetramine 80 Water i l 200.

- Refluxing' is continued' (about 25 minutes) until the separated resinous phase gives a .7 inch string from a coldplate.

The product which is a mixture of. a liquid resin phasemnd an aqueous phase is added to Grams Wood flour ground to pass 60 mesh) linoleum grade -4. 1200 Zinc stear e 24 andthoroughly mixed. The mixture is extruded,

dried and ground as in Example 2. The'result- .ing product has an apparent density of 029.

-. The mixture dried without extrusion has an give a bulky, fluffy, moist product in which. the

resin and wood'flour afe' intimately mixed.

The bulky mixer is igwpput into an extrusion" to apparent density of 0.21. p

Thermosettlng resins other than the phenol aldehyde type are suitable for use in the manufacture of molding compositions of thepresent invention and to this end urea aldehyde resins, as

well as other types of thermosetting natural and synthetic resins, may be employed.

- Example 4 A resin is prepared by heating for 1 hour at boiling temperature a mixtureof Grams Urea 600 37% formaldehyde 1400 Triethanolamine 12 p The product is mixed as before with 4 Grams Fine wood ilour (ground to pass mesh) 900 Stearic n 1 10 After extrusion and drying and grinding as Example 2, the. molding powder has an apparent Dried without extrusion, the

density of 0.25.- molding powder has an apparent density 010.20.

The present invention is of especial applicabil- Y ity in the production of a thermosetting molding composition containing long fiber filler, i. e. fillers such as chopped cord, cotton fioc, threads, and long rolled asbestos fiber. Molding compopositions of thermosetting resin and a filler of this type are fiuify and have a low apparent density due to the nature of the filler and due to the fact that rolled sheets when pulverized 'whisker so that much of uncovered.

To produce high density pellets or rods of long fiber filler, the filler of this type is mixed with the liquid resin and extruded as described. To get good orientation of the fibers, the length of the fiber is free and travel through the extrusion mold should be moderately great and at least about /8"; the greater 'the length of travel, the better the orientation.

The rods after extrusion and while still atan elevated temperature are placed in a tumbler and tumbled about. During this process, the rods are broken up and any free fiber extending outwardly from thesurfaceof the rods ispressed .into and held within the rods, furthermore, any voids dueto removal of liquid are eliminated and the density increased. After tumbling, the rods are dried, as indicated, -hereinbefore. The apparent density of the dried, tumbled rods with chopped cord as filler possessed a density of 0.29 gm./oc. as against 0.15 gm./cc. when made into sheets-and ground.

From the foregoing it will be seen that the invention provides a method for making a high density molding composition from long fibered filler, a composition wherein. excellent coverage of mix containing at least about 10% moisture,

forming the mix into pellets, removing water from the pellets and tumbling the pellets until their density has increased considerably without destroying the thermosetting characteristics thereof.

2. The method of making a thermosetting molding compound which comprises mixing an aqueous dispersion of a thermosetting resin and filler to form a'plastic mix,forming the mix into rods and thereafter tumbling the rods until a considerable increase in density has occurred, the

rods still retaining their thermosetting properties.

3. The method of making a thermosetting molding compound which comprises forming an aqueous dispersion of a thermosetting resin and filler into pellets containing considerable water and thereafter drying and tumbling the pellets until a considerable increase in derisity has occurred without destroying their thermosetting characteristics.

- HARRY M. DENT.

SYDNEY H. HALL. LOTHAR A. SONTAG. 

